CN109678172A - A kind of preparation method of titaniferous MWW structure molecular screen and its application of catalysis epoxidation - Google Patents
A kind of preparation method of titaniferous MWW structure molecular screen and its application of catalysis epoxidation Download PDFInfo
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- CN109678172A CN109678172A CN201910018984.9A CN201910018984A CN109678172A CN 109678172 A CN109678172 A CN 109678172A CN 201910018984 A CN201910018984 A CN 201910018984A CN 109678172 A CN109678172 A CN 109678172A
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- titaniferous
- mww
- molecular sieve
- molecular screen
- erb
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- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 22
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000002808 molecular sieve Substances 0.000 claims abstract description 98
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 49
- 239000010936 titanium Substances 0.000 claims abstract description 45
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052796 boron Inorganic materials 0.000 claims abstract description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 14
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 13
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 11
- -1 titanium halide Chemical class 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 7
- 239000012670 alkaline solution Substances 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 44
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 30
- LIKMAJRDDDTEIG-UHFFFAOYSA-N n-hexene Natural products CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 28
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims description 17
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 239000010453 quartz Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000443 aerosol Substances 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 5
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 5
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- OLGONLPBKFPQNS-UHFFFAOYSA-M sodium 2-(4-phenylphenyl)butanoate Chemical compound [Na+].CCC(C([O-])=O)c1ccc(cc1)-c1ccccc1 OLGONLPBKFPQNS-UHFFFAOYSA-M 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 150000003608 titanium Chemical class 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000012113 quantitative test Methods 0.000 claims description 2
- 125000005619 boric acid group Chemical group 0.000 claims 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 41
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 24
- 229920001296 polysiloxane Polymers 0.000 abstract description 10
- 238000001035 drying Methods 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 6
- 238000003780 insertion Methods 0.000 abstract description 3
- 230000037431 insertion Effects 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 24
- 150000003053 piperidines Chemical class 0.000 description 22
- 238000005406 washing Methods 0.000 description 22
- 239000000047 product Substances 0.000 description 20
- 239000013078 crystal Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 125000004429 atom Chemical group 0.000 description 16
- 238000013019 agitation Methods 0.000 description 15
- 230000008569 process Effects 0.000 description 13
- 238000002156 mixing Methods 0.000 description 12
- 238000010926 purge Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229960000935 dehydrated alcohol Drugs 0.000 description 9
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 8
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- LPCWMYHBLXLJJQ-UHFFFAOYSA-N 3-hexen-2-one Chemical compound CCC=CC(C)=O LPCWMYHBLXLJJQ-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- WQVHBNPUCCOUSZ-UHFFFAOYSA-N cyclohexene;2-hydroperoxy-2-methylpropane Chemical compound CC(C)(C)OO.C1CCC=CC1 WQVHBNPUCCOUSZ-UHFFFAOYSA-N 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- SIOHXTVHZFWRDC-UHFFFAOYSA-N OO.C=CCCCC Chemical compound OO.C=CCCCC SIOHXTVHZFWRDC-UHFFFAOYSA-N 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 4
- 238000011017 operating method Methods 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007033 dehydrochlorination reaction Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- QQKYFCAJVVQWPC-UHFFFAOYSA-N Cl.[B] Chemical compound Cl.[B] QQKYFCAJVVQWPC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- UQGNORZJBSUDEX-UHFFFAOYSA-N [B].OS(O)(=O)=O Chemical compound [B].OS(O)(=O)=O UQGNORZJBSUDEX-UHFFFAOYSA-N 0.000 description 1
- DHDQMKSHUONQDT-UHFFFAOYSA-N [B].[N+](=O)(O)[O-] Chemical compound [B].[N+](=O)(O)[O-] DHDQMKSHUONQDT-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
- C01B39/085—Group IVB- metallosilicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7088—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention provides a kind of preparation method of titaniferous MWW structure molecular screen and its application of catalysis epoxidation, is related to technical field of molecular sieve.The present invention is the following steps are included: (1) mixes borosilicate type MWW molecular sieve ERB-1 with modified solution, pyroreaction, boron removal molecular sieve D-ERB-1 is obtained, modified solution is one of the acid solution of 4 ~ 8 mol/L, the alkaline solution of 0.2-0.9mol/L, acid and its mixed solution of salt；(2) boron removal molecular sieve D-ERB-1 is placed in reactor, at 300 ~ 600 DEG C, brings reactor into using the titanium halide gas that nitrogen will volatilize saturated vapour pressure in device；(3) molecular sieve after reaction is set into alcoholysis, obtains titaniferous MWW structure molecular screen Ti-D-ERB-1 through drying, roasting.Titanium source carries out reacting insertion MWW structure with the silicone hydroxyl nest after boron removal in the form of titanium halide gas in the present invention, and titanium atom and hydroxyl nest are reacted into skeleton, are tightly combined.The Ti content controllability of addition is strong, and the catalyst of synthesis can be catalyzed bigger molecule, hydrogen peroxide does the epoxidation reaction of oxidant.
Description
Technical field
The present invention relates to technical field of molecular sieve, and in particular to a kind of preparation method of titaniferous MWW structure molecular screen and its
The application of catalysis epoxidation.
Background technique
Molecular sieve is a kind of inorganic crystal material with molecular dimension aperture or hole, it is with oxygen-octahedron and alumina
Tetrahedron (or containing other heteroatomic insertions) is basic structural unit, forms tridimensional network with shared oxygen atom.Due to
Its regular cellular structure, stable solid acid, higher hydrothermal stability and big specific surface area and hetero atom are embedded in band
The functional structure come becomes a kind of catalyst haveing excellent performance and adsorbent and is widely used in oil and gas processing, essence
Work, environmental protection etc. are refined, functional material important in modern industry is become.
There are two mutually independent 10 membered oxygen rings sine ducts for MWW family molecular sieves tool, and one of duct contains one 12
The supercage of membered oxygen rings, in addition having entrance on the surface of crystal is the bowl-shape hole of 12 membered oxygen rings, and not only structure is only for the molecular sieve
Spy, and since it derives from stratiform presoma, structure has the characteristics that plasticity and modifiability are strong, possesses unique topology
Structure.The main Types of MWW family molecular sieves have Si-Al molecular sieve MCM-22, SSZ-25, PSH-3, MCM-49, MCM-56, pure silicon
Molecular sieve ITQ-1, borosilicate zeolite ERB-1 etc..Wherein, MCM-22, PSH-3, SSZ-25, MCM-49 and ERB-1 interlayer are with oxygen
Bridge is connected, and is tightly combined, cannot change interfloor distance under the action of the solvent；But the precursor before MCM-22 and ERB-1 calcining
Coating combination is weaker, can change interfloor distance under the action of sweller, may be used as preparing layer column type molecular sieve MCM-36
Raw material；And MCM-56 is then a kind of lamellar zeolite with MWW single layer structure, B acid position exposure ratio is higher, and ITQ-2
It is a kind of single layer MWW molecular sieve structure that removing obtains.
The patent of nineteen ninety Mobil company makes public for the first time the synthetic method of MCM-22 and its diffraction pattern of XRD and diffraction
Data [U.S.4954325]；Corma etc. [Zeolites, 1996,16,7] confirms the knot of SSZ-25 by electron diffraction technique
Structure is closely similar with MCM-22.Bellussi in 1988 etc. [Eur. Pat. Appl. EPA 293032] just uses piperidines
(PI) borosilicate MWW molecular sieve, i.e. ERB-1 have been synthesized for template.1994, Mobile company passed through to low silica-alumina ratio MCM-22
It is swollen and is added SiO2It is supported and is obtained the MWW molecular sieve MCM-36 of layer column structure, is structurally characterized in that with MWW
Basic " two-layer structure " of molecular sieve, but in " interlayer structure " position of MWW with SiO2Support, and formed and possess 2.5 ~ 3nm's
Macropore [Microporous and Mesoporous Materials, 1998,25,207].Just because of MWW structure molecular screen
A large amount of active sites present in unique cellular structure and 12MR glasss, make it show huge application prospect in catalytic field.
Titanium Sieve Molecular Sieve is the hetero-atom molecular-sieve that titanium atom same order elements framework of molecular sieve silicon or aluminium obtain, and is matched due to four
Position titanium is in the isolated state of high degree of dispersion, there is common molecular to sieve no catalytic performance, especially in catalysis liquid phase hydro carbons
Good advantage is shown in terms of selective oxidation.Synthetic method about MWW structure titanium silicon molecular sieve at present, after mostly using
Manage synthetic method.Corma etc. [Chem. Commun., 1999,779] uses N, N, N- trimethyl -1- adamantane ammonium hydroxide and
Hexamethylene imine does template, and silicon dioxide aerosol is silicon source, pure silicon stratiform ITQ-2 presoma is prepared, with the side of grafting
Organic silicon source is grafted on presoma and obtains Ti/ITQ-2 by method.United States Patent (USP) 6759540 and Wu Peng etc.
[ZL200710037012.1] boric acid is added in the gel of preparation is done crystallization in motion agent using hydro-thermal method, with hexamethylene imine or
Piperidines is structure directing agent, takes the lead in successfully synthesizing titanium silicon MWW molecular sieve Ti-MWW-D.Tatsumi seminar [Chem.
Lett., 2000,29,774] synthesize B-MWW molecular sieve first, it, will be exhausted big in molecular sieve then by multiple pickling
Most boron are washed off, and due to the position vacancy of boron, lattice generates defective bit, then with piperidines (PI) or HMI as structure directing
Agent, the source Ti is added, and hydrothermal crystallizing, Ti enter lattice defect position again, to form Ti-MWW-P molecular sieve.
But Titanium Sieve Molecular Sieve Ti atom defective tightness in conjunction with framework of molecular sieve of these methods preparation is easy to be lost, make
It is reduced at molecular sieve activity, and needs secondary hydro-thermal that could synthesize molecular sieve containing Ti, the time that secondary hydro-thermal needs is long, production week
Phase is long, and preparation flow is complicated, and cost of material is higher, limits the use of molecular sieve.
Summary of the invention
In view of this, the present invention provides a kind of preparation method of titaniferous MWW structure molecular screen and its answering for catalysis epoxidation
With.The method for mending titanium is reacted with molecular sieve using titanium halide gas after ERB-1 molecular sieve boron removal, titanium active sites, process flow is added
Simply, substantially increase combined coefficient, the titanium of addition is evenly distributed in MWW crystal structure, titanium atom reacted with hydroxyl nest into
Enter skeleton, be tightly combined, not easily run off, the stability and repeatability of catalyst are preferable.
A kind of preparation method of titaniferous MWW structure molecular screen of the present invention, comprising the following steps:
It (1) is in mass ratio 10:5 ~ 30:5 ~ 30:50 ~ 500 ratio by silicon source, boron source, template and water using piperidines as template
Example, is fitted into autoclave, crystallization 3 ~ 9 days under 150 ~ 175 DEG C of dynamic conditions, products therefrom is washed after being mixed into colloidal
Wash, filter after dry, then borosilicate type MWW molecular sieve, i.e. ERB-1 are obtained after 450 ~ 650 DEG C of 3 ~ 18h of roasting.
The silicon source is one of silicon dioxide aerosol, silica lyosol, white carbon black or a variety of, the boron source
For one or both of boric acid, diboron trioxide.
(2) after ERB-1 being handled a period of time with modified solution hybrid reaction, washed, filtering is dried, through 450 ~ 650
Boron removal molecular sieve D-ERB-1 is obtained after DEG C 3 ~ 18h of roasting, and the modified solution is the acid solution that concentration is 4 ~ 8 mol/L, dense
Degree is one of alkaline solution, acid and its mixed solution of salt of 0.2-0.9mol/L；
Wherein, acid solution is one of nitric acid, hydrochloric acid, phosphoric acid, acetic acid or a variety of；Alkaline solution is tetramethyl hydroxide
One of ammonium, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, sodium hydroxide are a variety of.
(3) boron removal molecular sieve D-ERB-1 is placed in quartz tube reactor, whole process is maintained at 40 ~ 240 ml/ with flow
Min dry nitrogen purges, and 1 ~ 5 h is pre-processed at 200 ~ 600 DEG C, under 300 ~ 600 DEG C of reaction temperatures, nitrogen will volatilize device
In vapour pressure be 0.1 ~ 10 kPa the titanium halide gas of saturated vapour pressure bring in reactor 0.5 ~ 24 h time of reaction into, instead
It should terminate nitrogen and persistently purge a period of time, cooled to room temperature；
Halogenated titanium can be titanium tetrachloride, titanium tetrabromide or titanium tetrafluoride.
(4) molecular sieve after reaction is placed in 1 ~ 12h of alcoholysis time in dehydrated alcohol, after washing, filtering, dry, roasting
To the MWW molecular sieve of titaniferous.
Reaction principle: through acid or alkali process, the B-O key in molecular sieve crystal in Si-O-B key is easily broken, and tetrahedron is matched
The boron atom of position is to be removed, the hydroxyl nest for forming atom vacancy and being surrounded by four silicone hydroxyls (Si-OH), gaseous titanium halide
De-hydrogen halide occurs with silicone hydroxyl nest, forms Ti-O-Si key, titanium atom successfully occupies atom vacancy position and enters molecular sieve crystalline substance
Body skeleton.Compared to conventional hydrothermal synthetic method or after synthesize facture, do not need the high pressure hydro-thermal of prolonged secondary hydro-thermal
Reaction, generated time can be completed within 1-2 days, and Ti atom is successfully entered in framework of molecular sieve.By controlling N2Flow velocity and
The saturated vapour pressure of halogenated titanium, can control N2What is carried is volatilized into gaseous titanium source content, thus the titanium atom of controllable transplanting
The co-ordination state of content and titanium.The titanium of addition is evenly distributed in MWW crystal structure, and titanium atom and hydroxyl nest are reacted into bone
Frame is tightly combined, and is not easily runed off, and the stability and repeatability of catalyst are preferable.
Titanium source carries out reacting insertion MWW structure with the silicone hydroxyl nest in molecular sieve in the form of titanium halide gas in the present invention,
Titanium atom successfully occupies atom vacancy position and enters molecular sieve crystal skeleton, and the titanium of addition is evenly distributed in MWW crystal structure, titanium
Atom and hydroxyl nest are reacted into skeleton, are tightly combined, not easily run off, and the stability and repeatability of catalyst are preferable, preparation
Period is short.
A kind of application of catalysis epoxidation of titaniferous MWW structure molecular screen will be the following steps are included: will contain as previously described
Titanium MWW structure molecular screen is added in flask, is added epoxidation reaction object, is condensed back stirring at 40 ~ 60 DEG C, is then centrifuged for
Or filtering, filtrate are added internal standard compound GC quantitative test, recycle titaniferous MWW structure molecular screen after filtration cakes torrefaction.
Wherein, epoxidation reaction object can be 1- hexene, acetonitrile, the mixture of hydrogen peroxide or cyclohexene, n-decane, uncle
The mixture of butylhydroperoxide.
Titaniferous MWW structure molecular screen catalysis prepared by the present invention is applied widely, both can be to the biggish ring of molecular volume
Hexene and tert-butyl hydroperoxide carry out epoxidation, can also environmentally protective hydrogen peroxide make oxidant epoxy carried out to 1- hexene
Change reaction, epoxide conversion ratio with higher and selectivity.
Figure of description
Fig. 1 is the titaniferous MWW molecule prepared in the embodiment of the present invention 1 using a kind of preparation method of titaniferous MWW structure molecular screen
The X-ray diffraction spectrogram of sieve；
Fig. 2 is the titaniferous MWW molecule prepared in the embodiment of the present invention 1 using a kind of preparation method of titaniferous MWW structure molecular screen
The infrared spectrogram of sieve；
Fig. 3 is the titaniferous MWW molecule prepared in the embodiment of the present invention 1 using a kind of preparation method of titaniferous MWW structure molecular screen
The UV-vis DRS figure of sieve.
Specific embodiment
The present invention will be described in detail With reference to embodiment.
Embodiment one
A kind of preparation method of titaniferous MWW structure molecular screen, includes the following steps:
(1) 360g deionized water is added into polytetrafluoroethyllining lining, sequentially adds 36g piperidines, 36g tri- under agitation
Two boron and 36g silica lyosol are aoxidized, wherein Si:B:PI:H2The mass ratio of O is 10:10:10:100, by inside lining filling
Enter in high-temperature high-pressure reaction kettle, reaction kettle is in rotary oven crystallization 7 days under 175 DEG C of dynamic conditions；Products therefrom is washed, mistake
Filter, drying, finally 550 DEG C of roasting 6h obtain ERB-1 molecular sieve in Muffle furnace, and heating rate is 10 DEG C/min；
(2) 5g ERB-1 is mixed with 250ml 0.2mol/L sodium hydroxide solution and is added in 500ml flask, under agitation
22h is reacted in 100 DEG C of condensing refluxes, washing, filtering, dry, finally 550 DEG C of roasting 6h obtain the MWW of boron removal in Muffle furnace
Molecular sieve, heating rate are 10 DEG C/min；
(3) the MWW molecular sieve of 3g boron removal is placed in quartz tube reactor, whole process is purged with 100ml/min nitrogen, at 500 DEG C
3 h are pre-processed, reactor is maintained 500 DEG C, anhydrous titanium tetrachloride solution is added in glass volatilizer, volatilizer access is anti-
Device device is answered, volatilizer temperature is adjusted, so that the saturated vapor of titanium tetrachloride is pressed in 10kPa, nitrogen brings titanium tetrachloride vapors into
Reactor reaction 6h, reaction terminate nitrogen and persistently purge 5h, cooled to room temperature；
(4) molecular sieve after reaction is placed in alcoholysis 12h in dehydrated alcohol, washing, filtering, it is dry, finally 550 DEG C in Muffle furnace
Roasting 6h obtains the MWW molecular sieve of titaniferous, and heating rate is 10 DEG C/min.
The present embodiment from the silicon boron MWW structure molecular screen ERB-1 of dynamic autoclaved technology be starting point, through naoh treatment,
The boron atom of tetrahedral coordination is removed, the hydroxyl nest for forming atom vacancy and being surrounded by four silicone hydroxyls (Si-OH), gaseous state four
Dehydrochlorination reaction occurs for titanium chloride and silicone hydroxyl nest, and titanium atom successfully occupies atom vacancy position and enters molecular sieve crystal skeleton,
Obtain titaniferous MWW structure molecular screen；By Fig. 1 to Fig. 3 it is found that being confirmed by XRD, FT-IR, UV-Vis characterization method: it is crystallized
Degree reaches 99% or more, and crystal form is perfect, and surface is smooth, and titanium source is successfully entered skeleton and exists in the form of four-coordination.Its Si/Ti
=28。
Titaniferous MWW structure molecular screen manufactured in the present embodiment is applied to catalysis 1- hexene hydrogen peroxide epoxidation reaction, tool
Body operating procedure are as follows: 25ml round-bottomed flask net weight is weighed, titaniferous MWW structure molecular screen obtained by 0.05g is taken to be added in flask,
10mmol 1- hexene, 10ml acetonitrile, 10mmol hydrogen peroxide are sequentially added, stirring 3h, reaction knot are condensed back at 40 DEG C
Beam weighs flask gross weight after standing 30min, and filtering weighs filtrate, and 0.2g internal standard compound is added, is quantitatively examined with GC after mixing
It surveys, 1- hexene conversion ratio is 35.16%, and epoxidation product is selectively 100%.
Titaniferous MWW structure molecular screen manufactured in the present embodiment is applied to catalysis cyclohexene tert-butyl hydroperoxide epoxidation
Reaction, concrete operation step are as follows: weigh 25ml round-bottomed flask net weight, titaniferous MWW structure molecular screen obtained by 0.05g is taken to be added to
In flask, 10mmol cyclohexene, 5ml n-decane, 10mmol tert-butyl hydroperoxide are sequentially added, is condensed at 55 DEG C
Return stirring 3h, reaction terminate to weigh flask gross weight after standing 30min, and filtering weighs filtrate, and 0.2g internal standard compound, mixing is added
GC quantitative detection is used after uniformly, molecular sieve is recycled after filtration cakes torrefaction, and cyclohexene conversion rate is 41.02%, epoxidation product selectivity
It is 89.69% and with 6.15% by-product cyclic hexenone and 4.16% cyclohexanediol.
Embodiment two
A kind of preparation method of titaniferous MWW structure molecular screen, includes the following steps:
(1) 170g deionized water is added into polytetrafluoroethyllining lining, sequentially adds 54g piperidines, 18g boron under agitation
Acid and 18g silicon dioxide aerosol, wherein Si:B:PI:H2The mass ratio of O is 10:30:30:500, and liner is packed into high temperature
In autoclave, reaction kettle is in rotary oven crystallization 6 days under 175 DEG C of dynamic conditions；Products therefrom is washed, filtering, does
Dry, finally 550 DEG C of roasting 10h obtain ERB-1 molecular sieve in Muffle furnace, and heating rate is 10 DEG C/min；
(2) 3g ERB-1 is mixed with 150ml 0.9mol/L tetramethyl ammonium hydroxide solution and is added in 250ml flask, stirred
Under the conditions of in 100 DEG C of condensing refluxes react 20h, washing, filtering, dry, finally 550 DEG C of roasting 10h are taken off in Muffle furnace
The MWW molecular sieve of boron, heating rate are 10 DEG C/min；
(3) the MWW molecular sieve of 2g boron removal is placed in quartz tube reactor, whole process is purged with 40ml/min nitrogen, at 500 DEG C
3 h are pre-processed, reactor is warming up to 600 DEG C, anhydrous titanium tetrafluoride solution is added in glass volatilizer, volatilizer access is anti-
Device device is answered, volatilizer temperature is adjusted, so that the saturated vapor of titanium tetrafluoride is pressed in 0.1kPa, nitrogen brings titanium tetrafluoride steam into
Reactor reaction 9h, reaction terminate nitrogen and persistently purge 5h, cooled to room temperature；
(4) molecular sieve after reaction is placed in alcoholysis 18h in dehydrated alcohol, washing, filtering, it is dry, finally 550 DEG C in Muffle furnace
Roasting 10h obtains the MWW molecular sieve of titaniferous, and heating rate is 10 DEG C/min.
The present embodiment from the silicon boron MWW structure molecular screen ERB-1 of dynamic autoclaved technology be starting point, through alkaline solution treatment, four
The boron atom of face body coordination is removed, the hydroxyl nest for forming atom vacancy and being surrounded by four silicone hydroxyls (Si-OH), gaseous state tetrafluoro
Change titanium and dehydrochlorination reaction occurs for silicone hydroxyl nest, titanium atom successfully occupies atom vacancy position and enters molecular sieve crystal skeleton, obtains
To titaniferous MWW structure molecular screen；Confirmed by XRD, FT-IR, UV-Vis characterization method: its crystallinity reaches 99% or more, crystalline substance
Type is perfect, and surface is smooth, and titanium source is successfully entered skeleton and in the form of four-coordination and hexa-coordinate coexist.Its Si/Ti=73.By four
Ammonium hydroxide replaces with the testing result and this reality of tetraethyl ammonium hydroxide, the molecular sieve that tetrapropylammonium hydroxide is prepared
The data for applying example are similar.
Titaniferous MWW structure molecular screen manufactured in the present embodiment is applied to catalysis 1- hexene hydrogen peroxide epoxidation reaction, tool
Body operating procedure are as follows: 25ml round-bottomed flask net weight is weighed, titaniferous MWW structure molecular screen obtained by 0.05g is taken to be added in flask,
10mmol 1- hexene, 10ml acetonitrile, 10mmol hydrogen peroxide are sequentially added, stirring 3h, reaction knot are condensed back at 40 DEG C
Beam weighs flask gross weight after standing 30min, and filtering weighs filtrate, and 0.2g internal standard compound is added, is quantitatively examined with GC after mixing
It surveys, recycles molecular sieve after filtration cakes torrefaction, 1- hexene conversion ratio, 12.61%, epoxidation product is selectively 100%.
Titaniferous MWW structure molecular screen manufactured in the present embodiment is applied to catalysis cyclohexene tert-butyl hydroperoxide epoxidation
Reaction, concrete operation step are as follows: weigh 25ml round-bottomed flask net weight, titaniferous MWW structure molecular screen obtained by 0.05g is taken to be added to
In flask, 10mmol cyclohexene, 5ml n-decane, 10mmol tert-butyl hydroperoxide are sequentially added, is condensed at 60 DEG C
Return stirring 3h, reaction terminate to weigh flask gross weight after standing 30min, and filtering weighs filtrate, and 0.2g internal standard compound, mixing is added
GC quantitative detection is used after uniformly, recycles molecular sieve after filtration cakes torrefaction, and measuring cyclohexene conversion rate is 10.05%, epoxidation product choosing
Selecting property is 93.02%, and with 6.98% by-product cyclic hexenone.
Embodiment three
A kind of preparation method of titaniferous MWW structure molecular screen, includes the following steps:
(1) 1350g deionized water is added into polytetrafluoroethyllining lining, sequentially adds 81g piperidines, 81g under agitation
Diboron trioxide and 27g silica lyosol, wherein Si:B:PI:H2The mass ratio of O is 10:30:30:500, by liner
It is fitted into high-temperature high-pressure reaction kettle, reaction kettle is in rotary oven crystallization 9 days under 175 DEG C of dynamic conditions；Products therefrom is washed,
Filtering, drying, finally 550 DEG C of roasting 10h obtain ERB-1 molecular sieve in Muffle furnace, and heating rate is 10 DEG C/min；
(2) 6g ERB-1 is mixed with 300ml 0.7mol/L sodium hydroxide solution and is added in 500ml flask, under agitation
For 24 hours in 100 DEG C of condensing reflux reactions, washing, filtering, dry, finally 550 DEG C of roasting 10h obtain the MWW of boron removal in Muffle furnace
Molecular sieve, heating rate are 10 DEG C/min；
(3) the MWW molecular sieve of 5g boron removal is placed in quartz tube reactor, whole process is purged with 200ml/min nitrogen, at 400 DEG C
3 h are pre-processed, reactor is maintained 500 DEG C, anhydrous titanium tetrachloride solution is added in glass volatilizer, volatilizer access is anti-
Device device is answered, volatilizer temperature is adjusted, so that the saturated vapor of titanium tetrachloride is pressed in 10kPa, nitrogen brings titanium tetrachloride vapors into
Reactor reaction 0.5h, reaction terminate nitrogen and persistently purge 5h, cooled to room temperature；
(4) molecular sieve after reaction is placed in alcoholysis 12h in dehydrated alcohol, washing, filtering, it is dry, finally 550 DEG C in Muffle furnace
Roasting 10h obtains the MWW molecular sieve of titaniferous, and heating rate is 10 DEG C/min.
The present embodiment from the silicon boron MWW structure molecular screen ERB-1 of dynamic autoclaved technology be starting point, through naoh treatment,
The boron atom of tetrahedral coordination is removed, the hydroxyl nest for forming atom vacancy and being surrounded by four silicone hydroxyls (Si-OH), gaseous state four
Dehydrochlorination reaction occurs for titanium chloride and silicone hydroxyl nest, and titanium atom successfully occupies atom vacancy position and enters molecular sieve crystal skeleton,
Obtain titaniferous MWW structure molecular screen；Confirmed by XRD, FT-IR, UV-Vis characterization method: its crystallinity reaches 99% or more,
Crystal form is perfect, and surface is smooth, and titanium source is successfully entered skeleton and exists in the form of four-coordination.Its Si/Ti=27.
Titaniferous MWW structure molecular screen manufactured in the present embodiment is applied to catalysis 1- hexene hydrogen peroxide epoxidation reaction, tool
Body operating procedure are as follows: 25ml round-bottomed flask net weight is weighed, titaniferous MWW structure molecular screen obtained by 0.05g is taken to be added in flask,
10mmol 1- hexene, 10ml acetonitrile, 10mmol hydrogen peroxide are sequentially added, stirring 3h, reaction knot are condensed back at 40 DEG C
Beam weighs flask gross weight after standing 30min, and filtering weighs filtrate, and 0.2g internal standard compound is added, is quantitatively examined with GC after mixing
It surveys, 1- hexene conversion ratio is 36.16%, and epoxidation product is selectively 100%.
Titaniferous MWW structure molecular screen manufactured in the present embodiment is applied to catalysis cyclohexene tert-butyl hydroperoxide epoxidation
Reaction, concrete operation step are as follows: weigh 25ml round-bottomed flask net weight, titaniferous MWW structure molecular screen obtained by 0.05g is taken to be added to
In flask, 10mmol cyclohexene, 5ml n-decane, 10mmol tert-butyl hydroperoxide are sequentially added, is condensed at 55 DEG C
Return stirring 3h, reaction terminate to weigh flask gross weight after standing 30min, and filtering weighs filtrate, and 0.2g internal standard compound, mixing is added
GC quantitative detection is used after uniformly, molecular sieve is recycled after filtration cakes torrefaction, and cyclohexene conversion rate is 42.02%, epoxidation product selectivity
It is 88.59% and with 6.35% by-product cyclic hexenone and 4.06% cyclohexanediol.
Example IV
A kind of preparation method of titaniferous MWW structure molecular screen, includes the following steps:
(1) 1350g deionized water is added into polytetrafluoroethyllining lining, sequentially adds 81 piperidines, 81g boron under agitation
Acid and 27g silicon dioxide aerosol, wherein SiO2: H3BO3: PI:H2The mass ratio of O is 10:30:30:500, and liner is packed into
In high-temperature high-pressure reaction kettle, reaction kettle is in rotary oven crystallization 9 days under 175 DEG C of dynamic conditions；Products therefrom washing, filtering,
Dry, finally 550 DEG C of roasting 10h obtain ERB-1 molecular sieve in Muffle furnace, and heating rate is 10 DEG C/min；
(2) the nitric acid mixed solution of 6g ERB-1 and 300ml 0.8mol/L zinc nitrate solution and 5ml 0.05mol/L is added
In 500ml flask, under agitation for 24 hours in the reaction of 100 DEG C of condensing refluxes, washing, filtering, it is dry, finally in Muffle furnace
550 DEG C of roasting 10h obtain the MWW molecular sieve of boron removal, and heating rate is 10 DEG C/min；
(3) the MWW molecular sieve of 5g boron removal is placed in quartz tube reactor, whole process is purged with 200ml/min nitrogen, at 400 DEG C
3 h are pre-processed, reactor is warming up to 500 DEG C, anhydrous titanium tetrabromide is added in glass volatilizer, volatilizer accesses reactor
Device adjusts volatilizer temperature, so that the saturated vapor of titanium tetrabromide is pressed in 0.5 kPa, nitrogen brings titanium tetrabromide steam instead into
Device is answered to react 5h, reaction terminates nitrogen and persistently purges 5h, cooled to room temperature；
(4) molecular sieve after reaction is placed in alcoholysis 12h in dehydrated alcohol, washing, filtering, it is dry, finally 550 DEG C in Muffle furnace
The MWW molecular sieve of 10h titaniferous is roasted, heating rate is 10 DEG C/min.
The present embodiment is starting point from the silicon boron MWW structure molecular screen ERB-1 of dynamic autoclaved technology, is mixed through nitric acid and its salt
Solution boron removal transplants finally by atom and titanium atom is transplanted in the defect sites surrounded by hydroxyl nest, obtains titaniferous MWW knot
Structure molecular sieve Ti-D-ERB-1.Confirmed by XRD, FT-IR, UV-Vis characterization method: its crystallinity reaches 99% or more, crystal form
Perfection, surface is smooth, and titanium source is successfully entered skeleton and is coexisted in the form of four-coordination and hexa-coordinate, Si/Ti=39.
Titaniferous MWW structure molecular screen manufactured in the present embodiment is applied to catalysis 1- hexene hydrogen peroxide epoxidation reaction, tool
Body operating procedure are as follows: 25ml round-bottomed flask net weight is weighed, titaniferous MWW structure molecular screen obtained by 0.05g is taken to be added in flask,
10mmol 1- hexene, 10ml acetonitrile, 10mmol hydrogen peroxide are sequentially added, stirring 3h, reaction knot are condensed back at 40 DEG C
Beam weighs flask gross weight after standing 30min, and filtering weighs filtrate, and 0.2g internal standard compound is added, is quantitatively examined with GC after mixing
It surveys, molecular sieve is recycled after filtration cakes torrefaction, 1- hexene conversion ratio is 22.58%, and epoxy product is selectively 100%.
Embodiment five
A kind of preparation method of titaniferous MWW structure molecular screen, includes the following steps:
(1) 135g deionized water is added into polytetrafluoroethyllining lining, sequentially adds 13.5g piperidines, 27g under agitation
Boric acid and 27g silicon dioxide aerosol, wherein SiO2: H3BO3: PI:H2The mass ratio of O is 10:10:5:50, and liner is packed into
In high-temperature high-pressure reaction kettle, reaction kettle is in rotary oven crystallization 3 days under 175 DEG C of dynamic conditions；Products therefrom washing, filtering,
Dry, finally 550 DEG C of roasting 10h obtain ERB-1 molecular sieve in Muffle furnace, and heating rate is 10 DEG C/min；
(2) by the nickel nitrate solution of 6g ERB-1 and 0.1 mol/L of 300ml, the mixing of 10 ml, 0.5 mol/L nitric acid solution adds
Enter in 500ml flask, under agitation for 24 hours in 100 DEG C of condensing reflux reactions, washing filters, is dry, finally in Muffle furnace
In 550 DEG C of roasting 10h obtain the MWW molecular sieve of boron removal, heating rate is 10 DEG C/min；
(3) the MWW molecular sieve of 5g boron removal is placed in quartz tube reactor, whole process is purged with 200ml/min nitrogen, at 200 DEG C
3 h are pre-processed, reactor is warming up to 300 DEG C, anhydrous titanium tetrachloride is added in glass volatilizer, volatilizer accesses reactor
Device adjusts volatilizer temperature, so that the saturated vapor of titanium tetrachloride is pressed in 8kPa, nitrogen brings titanium tetrachloride vapors into reactor
16 h are reacted, reaction terminates nitrogen and persistently purges 5h, cooled to room temperature；
(4) molecular sieve after reaction is placed in alcoholysis 1h in dehydrated alcohol, washing, filtering, it is dry, finally 550 DEG C in Muffle furnace
The MWW molecular sieve of 10h titaniferous is roasted, heating rate is 10 DEG C/min.
The present embodiment is starting point from the silicon boron MWW structure molecular screen ERB-1 of dynamic autoclaved technology, is taken off through nitrate solution
Boron is transplanted finally by atom and titanium atom is transplanted in the defect sites surrounded by hydroxyl nest, obtains titaniferous MWW structural molecule
Sieve Ti-D-ERB-1.Confirmed by XRD, FT-IR, UV-Vis characterization method: its crystallinity reaches 99% or more, and crystal form is perfect,
Surface is smooth, and titanium source is successfully entered skeleton and is coexisted in the form of four-coordination and hexa-coordinate.Its Si/Ti=13.
Titaniferous MWW structure molecular screen manufactured in the present embodiment is applied to catalysis cyclohexene tert-butyl hydroperoxide epoxidation
Reaction, concrete operation step are as follows: weigh 25ml round-bottomed flask net weight, titaniferous MWW structure molecular screen obtained by 0.05g is taken to be added to
In flask, 10mmol cyclohexene, 5ml n-decane, 10mmol tert-butyl hydroperoxide are sequentially added, is condensed at 60 DEG C
Return stirring 3h, reaction terminate to weigh flask gross weight after standing 30min, and filtering weighs filtrate, and 0.2g internal standard compound, mixing is added
GC quantitative detection is used after uniformly, molecular sieve is recycled after filtration cakes torrefaction, and cyclohexene conversion rate is 51.04%, epoxidation product selectivity
It is 91.28% and with 8.72% by-product cyclic hexenone.
Embodiment six
A kind of preparation method of titaniferous MWW structure molecular screen, includes the following steps:
(1) 135g deionized water is added into polytetrafluoroethyllining lining, sequentially adds 13.5 piperidines under agitation,
13.5g boric acid and 27g silicon dioxide aerosol, wherein SiO2: H3BO3: PI:H2The mass ratio of O is 10:5:5:50, by liner
It is fitted into high-temperature high-pressure reaction kettle, reaction kettle is in rotary oven crystallization 9 days under 175 DEG C of dynamic conditions；Products therefrom washing, mistake
Filter, drying, finally 550 DEG C of roasting 10h obtain ERB-1 molecular sieve in Muffle furnace, and heating rate is 10 DEG C/min；
(2) 6g ERB-1 is mixed with 300ml 4mol/L hydrochloric acid solution and is added in 500ml flask, under agitation in 100
DEG C it is condensed back reaction for 24 hours, washing, filtering, dry, finally 550 DEG C of roasting 10h obtain the MWW molecule of boron removal in Muffle furnace
Sieve, heating rate are 10 DEG C/min；
(3) the MWW molecular sieve of 5g boron removal is placed in quartz tube reactor, whole process is purged with 200ml/min nitrogen, at 600 DEG C
3 h are pre-processed, reactor is warming up to 300 DEG C, anhydrous titanium tetrachloride is added in glass volatilizer, volatilizer accesses reactor
Device adjusts volatilizer temperature, so that the saturated vapor of titanium tetrachloride is pressed in 1.3 kPa, nitrogen brings titanium tetrachloride vapors instead into
Answer device reaction for 24 hours, reaction terminates nitrogen and persistently purges 5h, cooled to room temperature；
(4) molecular sieve after reaction is placed in alcoholysis 8h in dehydrated alcohol, washing, filtering, it is dry, finally 550 DEG C in Muffle furnace
The MWW molecular sieve of 10h titaniferous is roasted, heating rate is 10 DEG C/min.
The present embodiment from the silicon boron MWW structure molecular screen ERB-1 of dynamic autoclaved technology be starting point, through hydrochloric acid boron removal, finally
It is transplanted by atom and titanium atom is transplanted in the defect sites surrounded by hydroxyl nest, obtain titaniferous MWW structure molecular screen Ti-D-
ERB-1.Confirmed by XRD, FT-IR, UV-Vis characterization method: its crystallinity reaches 99% or more, and crystal form is perfect, surface light
Sliding, titanium source is successfully entered skeleton and is coexisted in the form of four-coordination and hexa-coordinate.Its Si/Ti=12.5.
It is similar with notebook data that hydrochloric acid is replaced with into final data in the experiment of phosphoric acid, acetic acid.
Titaniferous MWW structure molecular screen manufactured in the present embodiment is applied to catalysis 1- hexene hydrogen peroxide epoxidation reaction, is claimed
25ml round-bottomed flask net weight is measured, takes titaniferous MWW structure molecular screen obtained by 0.05g to be added in flask, sequentially adds
10mmol 1- hexene, 10ml acetonitrile, 10mmol hydrogen peroxide, are condensed back stirring 3h at 60 DEG C, and reaction terminates to stand
Flask gross weight is weighed after 30min, filtering weighs filtrate, and 0.2g internal standard compound is added, and uses GC quantitative detection, filter cake after mixing
Molecular sieve is recycled after drying, 1- hexene conversion ratio is 23.90%, and epoxy product is selectively 100%.
Embodiment seven
A kind of preparation method of titaniferous MWW structure molecular screen, includes the following steps:
(1) 270g deionized water is added into polytetrafluoroethyllining lining, sequentially adds 27 piperidines, 27g boron under agitation
Acid and 27g white carbon black, wherein Si:B:PI:H2The mass ratio of O is 10:10:10:100, and liner is packed into high-temperature high-voltage reaction
In kettle, reaction kettle is in rotary oven crystallization 4 days under 175 DEG C of dynamic conditions；Products therefrom washing, filtering, drying, finally in horse
Not 550 DEG C of roasting 10h obtain ERB-1 molecular sieve in furnace, and heating rate is 10 DEG C/min；
(2) 6g ERB-1 is mixed with 300ml 6mol/L sulfuric acid solution and is added in 500ml flask, under agitation in 100
DEG C it is condensed back reaction for 24 hours, washing, filtering, dry, finally 550 DEG C of roasting 10h obtain the MWW molecule of boron removal in Muffle furnace
Sieve, heating rate are 10 DEG C/min；
(3) the MWW molecular sieve of 5g boron removal is placed in quartz tube reactor, whole process is purged with 100ml/min nitrogen, at 300 DEG C
3 h are pre-processed, reactor is warming up to 600 DEG C, anhydrous titanium tetrachloride is added in glass volatilizer, volatilizer accesses reactor
Device adjusts volatilizer temperature, so that the saturated vapor of titanium tetrachloride is pressed in 10kPa, nitrogen brings titanium tetrachloride vapors into reaction
Device reacts 10h, and reaction terminates nitrogen and persistently purges 5h, cooled to room temperature；
(4) molecular sieve after reaction is placed in alcoholysis 8h in dehydrated alcohol, washing, filtering, it is dry, finally 550 DEG C in Muffle furnace
The MWW molecular sieve of 10h titaniferous is roasted, heating rate is 10 DEG C/min.
The present embodiment from the silicon boron MWW structure molecular screen ERB-1 of dynamic autoclaved technology be starting point, through sulfuric acid boron removal, finally
It is transplanted by atom and titanium atom is transplanted in the defect sites surrounded by hydroxyl nest, obtain titaniferous MWW structure molecular screen Ti-D-
ERB-1.Confirmed by XRD, FT-IR, UV-Vis characterization method: its crystallinity reaches 99% or more, and crystal form is perfect, surface light
Sliding, titanium source is successfully entered skeleton and is coexisted in the form of four-coordination and hexa-coordinate.Its Si/Ti=23.
Titaniferous MWW structure molecular screen manufactured in the present embodiment is applied to catalysis cyclohexene tert-butyl hydroperoxide epoxidation
Reaction, concrete operation step are as follows: weigh 25ml round-bottomed flask net weight, titaniferous MWW structure molecular screen obtained by 0.05g is taken to be added to
In flask, 10mmol cyclohexene, 5ml n-decane, 10mmol tert-butyl hydroperoxide are sequentially added, is condensed at 60 DEG C
Return stirring 3h, reaction terminate to weigh flask gross weight after standing 30min, and filtering weighs filtrate, and 0.2g internal standard compound, mixing is added
GC quantitative detection is used after uniformly, molecular sieve is recycled after filtration cakes torrefaction, and cyclohexene conversion rate is 50.08%, epoxidation product selectivity
It is 95.77% and with 3.60% by-product cyclic hexenone and 0.64% cyclohexanediol.
Embodiment eight
A kind of preparation method of titaniferous MWW structure molecular screen, includes the following steps:
(1) 270g deionized water is added into polytetrafluoroethyllining lining, sequentially adds 27 piperidines, 27g boron under agitation
Acid and 27g white carbon black, wherein Si:B:PI:H2The mass ratio of O is 10:10:10:100, and liner is packed into high-temperature high-voltage reaction
In kettle, reaction kettle is in rotary oven crystallization 4 days under 175 DEG C of dynamic conditions；Products therefrom washing, filtering, drying, finally in horse
Not 550 DEG C of roasting 10h obtain ERB-1 molecular sieve in furnace, and heating rate is 10 DEG C/min；
(2) 5g ERB-1 is mixed with 260ml 8mol/L nitric acid solution and is added in 500ml flask, under agitation in 100
DEG C it is condensed back reaction for 24 hours, washing, filtering, dry, finally 550 DEG C of roasting 10h obtain the MWW molecule of boron removal in Muffle furnace
Sieve, heating rate are 10 DEG C/min；
(3) the MWW molecular sieve of 5g boron removal is placed in quartz tube reactor, whole process is purged with 100ml/min nitrogen, at 300 DEG C
3 h are pre-processed, reactor is warming up to 600 DEG C, anhydrous titanium tetrachloride is added in glass volatilizer, volatilizer accesses reactor
Device adjusts volatilizer temperature, so that the saturated vapor of titanium tetrachloride is pressed in 5kPa, nitrogen brings titanium tetrachloride vapors into reactor
10h is reacted, reaction terminates nitrogen and persistently purges 5h, cooled to room temperature；
(4) molecular sieve after reaction is placed in alcoholysis 8h in dehydrated alcohol, washing, filtering, it is dry, finally 550 DEG C in Muffle furnace
The MWW molecular sieve of 10h titaniferous is roasted, heating rate is 10 DEG C/min.
The present embodiment from the silicon boron MWW structure molecular screen ERB-1 of dynamic autoclaved technology be starting point, through nitric acid boron removal, finally
It is transplanted by atom and titanium atom is transplanted in the defect sites surrounded by hydroxyl nest, obtain titaniferous MWW structure molecular screen Ti-D-
ERB-1.Confirmed by XRD, FT-IR, UV-Vis characterization method: its crystallinity reaches 99% or more, and crystal form is perfect, surface light
Sliding, titanium source is successfully entered skeleton and is coexisted in the form of four-coordination and hexa-coordinate.Its Si/Ti=22.
Titaniferous MWW structure molecular screen manufactured in the present embodiment is applied to catalysis cyclohexene tert-butyl hydroperoxide epoxidation
Reaction, concrete operation step are as follows: weigh 25ml round-bottomed flask net weight, titaniferous MWW structure molecular screen obtained by 0.05g is taken to be added to
In flask, 10mmol cyclohexene, 5ml n-decane, 10mmol tert-butyl hydroperoxide are sequentially added, is condensed at 55 DEG C
Return stirring 3h, reaction terminate to weigh flask gross weight after standing 30min, and filtering weighs filtrate, and 0.2g internal standard compound, mixing is added
GC quantitative detection is used after uniformly, molecular sieve is recycled after filtration cakes torrefaction, and cyclohexene conversion rate is 49.18%, epoxidation product selectivity
It is 96.073% and with 3.50% by-product cyclic hexenone and 0.64% cyclohexanediol.
Present invention process process shortens, and substantially increases combined coefficient, the titanium of addition is distributed in MWW crystal structure
Even, titanium atom and hydroxyl nest are reacted into skeleton, are tightly combined, not easily run off, the stability of catalyst is preferable.Of the invention contains
The catalysis of titanium MWW structure molecular screen is applied widely, both can to the biggish cyclohexene of molecular volume and tert-butyl hydroperoxide into
Row epoxidation, can also environmentally protective hydrogen peroxide do oxidant to 1- hexene carry out epoxidation reaction, epoxy with higher
Compound ratio transformation and selectivity.
The present invention is not limited to above-mentioned specific embodiment, and the invention may be variously modified and varied.All foundations
Technical spirit of the invention should be included in the present invention to embodiment of above any modification, equivalent replacement, improvement and so on
Protection scope.
Claims (10)
1. a kind of preparation method of titaniferous MWW structure molecular screen, which comprises the following steps:
(1) borosilicate type MWW molecular sieve ERB-1 is mixed with modified solution, pyroreaction obtains boron removal molecular sieve D-ERB-1, institute
State modified solution be concentration be the acid solution of 4 ~ 8 mol/L, concentration be 0.2-0.9mol/L alkaline solution, acid and its salt
One of mixed solution；
(2) boron removal molecular sieve D-ERB-1 is placed in quartz tube reactor, at 300 ~ 600 DEG C, will volatilize device using nitrogen
The titanium halide gas of middle saturated vapour pressure brings reactor into, is reacted；
(3) for a period of time by the molecular sieve alcoholysis after reaction, washed, filtering, dry, roasting obtain titaniferous MWW structural molecule
Sieve Ti-D-ERB-1.
2. a kind of preparation method of titaniferous MWW structure molecular screen according to claim 1, which is characterized in that step (2) institute
Stating halogenated titanium is one of titanium tetrachloride, titanium tetrabromide, titanium tetrafluoride or a variety of.
3. a kind of preparation method of titaniferous MWW structure molecular screen according to claim 1, which is characterized in that step (1) institute
Stating acid solution is one of nitric acid, hydrochloric acid, phosphoric acid, acetic acid or a variety of.
4. a kind of preparation method of titaniferous MWW structure molecular screen according to claim 1, which is characterized in that step (1) institute
The alkaline solution stated be one of tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, sodium hydroxide or
It is a variety of.
5. a kind of preparation method of titaniferous MWW structure molecular screen according to claim 1, which is characterized in that in step (2)
It should be pre-processed at 200 ~ 600 DEG C before reactions.
6. a kind of preparation method of titaniferous MWW structure molecular screen according to claim 1, which is characterized in that step (2) institute
The saturated vapour pressure for stating halogenated titanium is 0.1 ~ 10 kPa.
7. a kind of preparation method of titaniferous MWW structure molecular screen according to claim 1, which is characterized in that step (1) institute
The preparation process of the borosilicate type MWW molecular sieve ERB-1 stated is the following steps are included: by silicon source, boron source, template and water according to matter
Amount obtains borosilicate type MWW molecular sieve ERB-1 after crystallization than being that the ratio of 10:5 ~ 30:5 ~ 30:50 ~ 500 mixes after roasting.
8. a kind of preparation method of titaniferous MWW structure molecular screen according to claim 7, which is characterized in that the silicon source
For one of silicon dioxide aerosol, silica lyosol, white carbon black or a variety of, the boron source is boric acid, three oxidations two
One or both of boron.
9. a kind of application of the catalysis epoxidation of titaniferous MWW structure molecular screen as described in any one of claim 1-8,
It is characterized in that, comprising the following steps: titaniferous MWW structure molecular screen is added in flask, adds epoxidation reaction object, 40 ~
It is condensed back stirring at 60 DEG C, is then centrifuged for or filters, internal standard compound GC quantitative test is added in filtrate, recycles after filtration cakes torrefaction
Titaniferous MWW structure molecular screen.
10. a kind of application of the catalysis epoxidation of titaniferous MWW structure molecular screen according to claim 9, which is characterized in that
The epoxidation reaction object is 1- hexene, acetonitrile, the mixture of hydrogen peroxide or cyclohexene, n-decane, tert-butyl hydroperoxide
Mixture.
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